Polymer Nanofilms
FULL PAPER
3
3
3
4
3J3,4 =4.2 Hz, 1H; 4-H), 2.41 ppm (s, 3H; Me); 13C NMR (100.69 MHz,
CDCl3): d=148.99 (C=N), 137.88 (C-5), 134.66 (C-2), 131.67 (C-3),
(dd, J3’,4’ =3.8 Hz, J5’,4’ =5.5 Hz, 1H; 4’-H), 7.14 (dd, J3’,4’ =3.8 Hz, J3’,5’ =
1.0 Hz, 1H; 3’-H), 6.78 (dd, 3J5,4 =2.7 Hz, 4J5,3 =1.3 Hz, 1H; 5-H), 6.37
(dd, 3J3,4 =3.6 Hz, 4J3,5 =1.3 Hz, 1H; 3-H), 6.23 ppm (dd, 3J3,4 =3.6 Hz,
3J5,4 =2.7 Hz, 1H; 4-H); 13C NMR (100.69 MHz, CDCl3): d=141.47 (C-
2’), 130.22 (C-4’), 127.79 (C-5’), 128.75 (C-2), 122.71 (C-3’), 118.86 (C-5),
110.26 (C-4), 107.55 ppm (C-3); IR (film): n˜ =3363, 1510, 1461, 1255,
1120, 1098, 1036, 987, 886, 817, 795, 786, 727, 680, 571 cmÀ1; elemental
analysis calcd (%) for C8H7NSe (196.11): C 49.00, H 3.60, N 7.14, Se
40.26; found: C 49.35, H 3.32, N 7.22, Se 40.63.
128.00 (C-4), 19.50 ppm (Me); NMR for
(400.13 MHz, CDCl3): d=9.67 (s, 1H; OH), 7.90 (dd, J5,4 =5.6 Hz, J5,3
E
isomer: 1H NMR
3
4
=
1.0 Hz, 1H; 5-H), 7.42 (dd, 3J3,4 =3.9 Hz, 4J3,5 =1.0 Hz, 1H; 3-H), 7.25
(dd, 3J5,4 =5.6 Hz, 3J3,4 =3.9 Hz, 1H; 4-H), 2.30 ppm (s, 3H; Me);
13C NMR (100.69 MHz, CDCl3): d=153.67 (C=N), 145.88 (C-2), 131.62
(C-5), 129.73 (C-4), 128.97 (C-3), 12.02 ppm (Me); IR (KBr): n˜ =1646,
1612, 1426, 1368, 1290, 1231, 1093, 1035, 993, 936, 832, 794, 698, 654,
450 cmÀ1; elemental analysis calcd (%) for C6H7NOSe (188.09): C 38.32,
H 3.75, N 7.45, Se 41.98; found: C 38.64, H 3.78, N 7.25, Se 41.70.
3-Methyl-2-(selenophen-2-yl)pyrrole (8): Oil; 1H NMR (400.13 MHz,
CDCl3): d=8.10 (s, 1H; NH), 7.86 (dd, 3J5’,4’ =5.6 Hz, 4J5’,3’ =1.0 Hz, 1H;
5’-H), 7.27 (dd, 3J3’,4’ =3.7 Hz, 3J5’,4’ =5.6 Hz, 1H; 4’-H), 7.11 (dd, J3’,4’
=
3
1-(2-Selenophenyl)-1-propanone oxime (5): Colourless crystals (86%);
m.p. 85–878C; Z/E 6:4; NMR for Z isomer: 1H NMR (400.13 MHz,
3.7 Hz, 4J3’,5’ =1.0 Hz, 1H; 3’-H), 7.00 (d, 3J5,4 =2.7 Hz, 1H; 5-H), 6.11 (d,
3J5,4 =2.7 Hz, 1H; 4-H), 2.26 ppm (s, 3H; Me); 13C NMR (100.69 MHz,
CDCl3): d=140.78 (C-2’), 130.06 (C-4’), 128.33 (C-5’), 125.12 (C-2),
123.74 (C-3’), 117.50 (C-5), 117.00 (C-3), 112.41 (C-4), 12.50 ppm (Me);
3
4
CDCl3): d=9.50 (s, 1H; OH), 8.33 (dd, J5,4 =5.6 Hz, J5,3 =1.0 Hz, 1H; 5-
3
4
3
H), 7.72 (dd, J3,4 =4.2 Hz, J3,5 =1.0 Hz, 1H; 3-H), 7.37 (dd, J4,5 =5.9 Hz,
3J3,4 =4.2 Hz, 1H; 4-H), 2.80 (q, 3J=7.5 Hz, 2H; CH2), 1.32 ppm (t, 3H;
Me); 13C NMR (100.69 MHz, CDCl3): d=152.53 (C=N), 137.12 (C-5),
133.65 (C-2), 130.62 (C-3), 127.51 (C-4), 26.40 (CH2), 12.02 ppm (Me);
IR (film): n˜ =3380, 1644, 1455, 1230, 1093, 844, 790, 736, 683, 519 cmÀ1
;
elemental analysis calcd (%) for C9H9NSe (210.13): C 51.44, H 4.32, N
6.67, Se 37.58; found: C 51.34, H 4.69, N 6.58, Se 37.36.
NMR for E isomer: 1H NMR (400.13 MHz, CDCl3): d=9.50 (s, 1H;
3
OH), 7.90 (dd, 3J5,4 =5.6 Hz, 4J5,3 =1.0 Hz, 1H; 5-H), 7.42 (dd, J3,4
=
3-Ethyl-2-(selenophen-2-yl)pyrrole (9): Oil; 1H NMR (400.13 MHz,
3.9 Hz, 4J3,5 =1.0 Hz, 1H; 3-H), 7.26 (dd, 3J5,4 =5.6 Hz, 3J3,4 =3.9 Hz, 1H;
4-H), 2.83 (q, 3J=7.5 Hz, 2H; CH2), 1.22 ppm (s, 3H; Me); 13C NMR
(100.69 MHz, CDCl3): d=157.9 (C=N), 144.74 (C-2), 131.07 (C-5), 129.26
(C-4), 128.07 (C-3), 19.51 (CH2), 10.82 ppm (Me); IR (KBr): n˜ =1633,
1623, 1463, 1426, 1370, 1289, 1254, 1225, 1093, 1064, 1024, 1007, 954, 922,
936, 871, 840, 795, 712, 690, 654, 467, 450 cmÀ1; elemental analysis calcd
(%) for C7H9NOSe (202.11): C 41.60, H 4.49, N 6.93, Se 39.07; found: C
41.81, H 4.66, N 7.04, Se 38.88.
CDCl3): d=8.06 (s, 1H; NH), 7.89 (dd, 3J5’,4’ =5.6 Hz, 4J5’,3’ =0.8 Hz, 1H;
5’-H), 7.29 (dd, 3J3’,4’ =3.7 Hz, 3J5’,4’ =5.6 Hz, 1H; 4’-H), 7.13 (dd, J3’,4’
=
3
3.7 Hz, 4J3’,5’ =0.8 Hz, 1H; 3’-H), 6.73 (d, 3J5,4 =3.0 Hz, 1H; 5-H), 6.21 (d,
3J5,4 =3.0 Hz, 1H; 4-H), 2.69 (q, 3J=7.6 Hz, 2H; CH2), 1.28 ppm (t, 3J=
7.6 Hz, 3H; Me); 13C NMR (100.69 MHz, CDCl3): d=140.21 (C-2’),
129.73 (C-4’), 128.16 (C-5’), 123.79 (C-2), 123.52 (C-3’), 123.40 (C-3),
117.39 (C-5), 109.56 (C-4), 19.59 (CH2), 14.75 ppm (Me); IR (film): n˜ =
3380, 2963, 2928, 2868, 1644, 1525, 1457, 1378, 1229, 1101, 990, 916, 893,
830, 786, 689 cmÀ1; elemental analysis calcd (%) for C10H11NSe (224.16):
C 53.58, H 4.95, N 6.25, Se 35.22; found: C 53.61, H 4.95, N 6.22, Se
34.99.
1-(2-Selenophenyl)-1-butanone oxime (6): Colourless crystals (82%);
m.p. 57–598C; Z/E 6:4; NMR for Z isomer: 1H NMR (400.13 MHz,
3
4
CDCl3): d=9.44 (s, 1H; OH), 8.33 (dd, J5,4 =5.6 Hz, J5,3 =1.0 Hz, 1H; 5-
3
4
3
H), 7.70 (dd, J3,4 =4.2 Hz, J3,5 =1.0 Hz, 1H; 3-H), 7.34 (dd, J4,5 =5.9 Hz,
3J3,4 =4.2 Hz, 1H; 4-H), 2.74 (q, 3J=7.5 Hz, 2H; CH2CH2), 1.75 (m, 2H;
CH2Me), 1.01 ppm (t, 3H; Me); 13C NMR (100.69 MHz, CDCl3): d=
152.10 (C=N), 137.43 (C-5), 134.20 (C-2), 131.14 (C-3), 127.92 (C-4),
Synthesis of 1-vinylpyrroles 10–12: The respective oximes (4–6;
2.66 mmol) and KOH·0.5H2O (173 mg, 2.66 mmol) were dissolved under
heating (808C) in DMSO (50 mL). The solution of potassium oximate
was placed in a 0.25 L rotating steel autoclave. The autoclave was filled
with acetylene from a cylinder to a pressure of 14 atm and then the acet-
ylene was released to remove air. The autoclave was charged once more
with acetylene to the same pressure and heated (1008C, 30 min) under
rotation. After treatment of the reaction mixture as described above,
pure 10–12 were obtained. For yields, see Scheme 1.
35.06 (CH2CH2), 20.90 (CH2Me), 14.53 ppm (Me); NMR for E isomer:
3
1H NMR (400.13 MHz, CDCl3): d=9.44 (s, 1H; OH), 7.89 (dd, J5,4
=
5.6 Hz, 4J5,3 =1.0 Hz, 1H; 5-H), 7.37 (dd, 3J3,4 =3.9 Hz, 4J3,5 =1.0 Hz, 1H;
3-H), 7.27 (dd, 3J5,4 =5.6 Hz, 3J3,4 =3.9 Hz, 1H; 4-H), 2.75 (q, 3J=7.5 Hz,
2H; CH2CH2), 1.69 (CH2Me), 1.00 ppm (s, 3H; Me); 13C NMR
(100.69 MHz, CDCl3): d=157.39 (C=N), 145.30 (C-2), 131.43 (C-5),
129.65 (C-4), 128.61 (C-3), 27.80 (CH2CH2), 19.85 (CH2Me), 13.86 ppm
(Me); IR (KBr): n˜ =1654, 1599, 1453, 1423, 1308, 1270, 1079, 1043, 994,
954, 923, 839, 794, 665, 641, 454 cmÀ1; elemental analysis calcd (%) for
C8H11NOSe (216.14): C 44.46, H 5.13, N 6.48, Se 36.53; found: C 44.61, H
5.11, N 6.10, Se 36.61.
2-(Selenophen-2-yl)-1-vinylpyrrole (10): Oil; 1H NMR (400.13 MHz,
CDCl3): d=7.98 (dd, 3J5’,4’ =5.6 Hz, 4J5’,3’ =1.0 Hz, 1H; 5’-H), 7.30 (dd,
3J3’,4’ =3.9 Hz, 3J5’,4’ =5.6 Hz, 1H; 4’-H), 7.12 (dd, 3J3’,4’ =3.9 Hz, J3’,5’
=
4
1.0 Hz, 1H; 3’-H), 7.09 (dd, 3J5,4 =3.1 Hz, 4J5,3 =1.7 Hz, 1H; 5-H), 7.08
(dd, 3JBX =15.7 Hz, 3JAX =8.8 Hz, 1H; HX), 6.32 (dd, 3J3,4 =3.7 Hz, J5,3
=
4
1.7 Hz, 1H; 3-H), 6.25 (dd, 3J3,4 =3.7 Hz, 3J5,4 =3.1 Hz, 1H; 4-H), 5.18
(dd, 3JBX =15.7 Hz, 2JAB =1.1 Hz, 1H; HB), 4.74 ppm (dd, 3JAX =8.8 Hz,
2JAB =1.1 Hz, 1H; HA); 13C NMR (100.69 MHz, CDCl3): d=138.95 (C-
2’), 131.50 (C-a), 131.08 (C-5’), 129.89 (C-4’), 128.79 (C-2), 128.77 (C-3’),
118.64 (C-5), 111.62 (C-3), 110.29 (C-4), 99.53 ppm (C-b); IR (film): n˜ =
3420, 2923, 1642, 1468, 1438, 1348, 1286, 1256, 1215, 1033, 989, 886, 812,
784, 718, 682, 582 cmÀ1; elemental analysis calcd (%) for C10H9NSe
(222.15): C 54.07, H 4.08, N 6.31, Se 35.54; found: C 54.19, H 4.09, N
6.42, Se 35.33.
Synthesis of 1H-pyrroles 7–9: The respective oxime (4–6; 2.66 mmol) and
NaOH (106 mg, 2.66 mmol) were dissolved under heating (808C) in
DMSO (50 mL). The solution of sodium oximate thus obtained was
placed in a 0.25 L rotating steel autoclave. The autoclave was filled with
acetylene from a cylinder to a pressure of 14 atm and then the acetylene
was released to remove air. The autoclave was charged with acetylene
once more to the same pressure and then heated (1008C, 60 min) under
rotation. The acetylene pressure peaked at 25 atm and then rapidly de-
creased due to the reaction of acetylene with the ketoxime. After cooling
to room temperature, the remaining pressure in the autoclave was 8 atm.
The reaction mixture was then diluted with a twofold volume excess of
iced water, neutralized with NH4Cl, and the resulting solution was ex-
tracted with diethyl ether (5ꢃ5 mL). The ethereal extracts were washed
with cold water (3ꢃ5 mL) to remove dissolved DMSO. The ethereal so-
lution was then dried over K2CO3 overnight. After evaporation of the
solvent, column chromatography of the residue (basic Al2O3) gave pure
ketones 1–3, 1H-pyrroles 7–9, and 1-vinylpyrroles 10–12. First, 1-vinylpyr-
roles 10–12 were eluted with hexane, then pyrroles 7–9 and finally ke-
tones 1–3 were eluted with the system hexane/diethyl ether (5:1). For
yields, see Scheme 1.
3-Methyl-2-(selenophen-2-yl)-1-vinylpyrrole
(11):
Oil;
1H NMR
(400.13 MHz, CDCl3): d=8.10 (dd, 3J5’,4’ =5.6 Hz, 4J5’,3’ =1.1 Hz, 1H; 5’-
H), 7.32 (dd, 3J3’,4’ =3.7 Hz, 3J5’,4’ =5.6 Hz, 1H; 4’-H), 7.10 (dd, J3’,4’
=
3
3.7 Hz, 4J3’,5’ =1.1 Hz, 1H; 3’-H), 7.03 (d, 3J5,4 =3.1 Hz, 1H; 5-H), 6.96
(dd, 3JBX =15.7 Hz, 3JAX =8.9 Hz, 1H; HX), 6.13 (d, 3J5,4 =3.1 Hz, 1H; 4-
H), 5.06 (dd, 3JBX =15.7 Hz, 2JAB =1.1 Hz, 1H; HB), 4.58 (dd, JAX
=
3
8.9 Hz, 2JAB =1.1 Hz, 1H; HA), 2.08 ppm (s, 3H; Me); 13C NMR
(100.69 MHz, CDCl3): d=137.90 (C-2’), 132.71 (C-5’), 131.68 (C-a),
131.30 (C-3’), 129.59 (C-4’), 125.13 (C-2), 120.46 (C-3), 117.02 (C-5),
111.95 (C-4), 97.52 (C-b), 12.15 ppm (Me); IR (film): n˜ =2964, 2918,
2850, 1639, 1475, 1452, 1388, 1369, 1330, 1305, 1297, 1229, 1186, 1080,
1009, 963, 911, 859, 836, 813, 788, 723, 688, 666, 624, 591, 458 cmÀ1; ele-
mental analysis calcd (%) for C11H11NSe (236.18): C 55.94, H 4.69, N
5.93, Se 33.43; found: C 56.12, H 4.69, N 5.69, Se 33.28.
2-(Selenophen-2-yl)pyrrole (7): Oil; 1H NMR (400.13 MHz, CDCl3): d=
8.34 (s, 1H; NH), 7.78 (dd, 3J5’,4’ =5.5 Hz, 4J5’,3’ =1.0 Hz, 1H; 5’-H), 7.21
Chem. Eur. J. 2009, 15, 6435 – 6445
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6443